Carboxamide compound and use of the same

ABSTRACT

A carboxamide compound represented by the formula (I): 
                         
[wherein Q represents a nitrogen-containing 5-membered heterocyclic group optionally fused with a benzene ring, R 1  represents a C1-C3 alkyl group or the like, R 2  represents a hydrogen atom or the like, and R 3  represents a hydrogen atom.] has an excellent plant disease controlling effect.

This application is a Divisional of application Ser. No. 11/919,077filed Oct. 23, 2007 (which issued as U.S. Pat. No. 7,935,716 B1 on May3, 2011) for which priority is claimed under 35 U.S.C. §120, which isthe national phase of PCT International. Application No.PCT/JP2006/308500 filed on Apr. 18, 2006 under 35 U.S.C. §371. Theentire contents of each of the above-identified applications are herebyincorporated by reference.

TECHNICAL FIELD

The present invention relates to a carboxamide compound, and use of thesame.

BACKGROUND ART

Development of a plant disease controlling agent has been progressed,and many compounds having controlling activity against plant diseaseshave been found out. However, plant disease controlling activity ofthese compounds is not sufficient in some cases.

Novel compounds having plant disease controlling activity have beeninvestigated intensively.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a compound havingexcellent plant disease controlling activity.

The present invention is as follows:

[1] A carboxamide compound represented by the formula (I):

[wherein Q represents a nitrogen-containing 5-membered heterocyclicgroup optionally fused with a benzene ring, and the heterocyclic groupmay be substituted with at least one group selected from the groupconsisting of a halogen atom, a cyano group, a C1-C3 alkyl group and aC1-C3 haloalkyl group, R¹ represents a C1-C3 alkyl group or a C2-C5alkoxyalkyl group, R² represents a hydrogen atom or a C1-C3 alkyl group,or R¹ and R² bind to each other at an end to represent a C3-C4 alkylenegroup and R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkylgroup.] (hereinafter, referred to as present compound).

[2] The carboxamide compound according to [1], wherein Q is anitrogen-containing 5-membered heterocyclic group optionally fused witha benzene ring, and the heterocyclic group may be substituted with atleast one group selected from the group consisting of a halogen atom, acyano group, a C1-C3 alkyl group and a C1-C3 haloalkyl group, and acarbon atom adjacent to a nitrogen atom among ring constitutional atomsand a nitrogen atom of NH in the formula (I) bind to each other.

[3] The carboxamide compound according to [1], wherein Q is anitrogen-containing 5-membered heterocyclic group optionally fused witha benzene ring, the heterocyclic group may be substituted with at leastone group selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group, and theheterocyclic group has as a ring constitutional atom one nitrogen atom,and at least one hetero atom selected from an oxygen atom, a sulfur atomand a nitrogen atom.

[4] The carboxamide compound according to [1], wherein Q is anitrogen-containing 5-membered heterocyclic group not fused with otherring, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group.

[5] The carboxamide compound according to [1], wherein Q is anitrogen-containing 5-membered heterocyclic group fused with a benzenering, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group.

[6] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a thiazolyl group, a benzothiazolyl group,an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a1,2,4-oxadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,2,4-triazolylgroup, a 1,3,4-oxadiazolyl group or a 1,3,4-thiadiazolyl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group.

[7] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-thiazolyl group, a 2-benzothiazolylgroup, a 2-imidazolyl group, a 2-benzimidazolyl group, a 3-pyrazolylgroup, a 1,2,4-oxadiazol-5-yl group, a 1,2,4-thiadiazol-5-yl group, a1,2,4-triazol-3-yl group, a 1,3,4-oxadiazol-2-yl group or a1,3,4-thiadiazol-2-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and C1-C3haloalkyl group.

[8] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-thiazolyl group, a 2-imidazolyl group, a3-pyrazolyl group, a 1,2,4-oxadiazol-5-yl group, a 1,2,4-thiadiazol-5-ylgroup, a 1,2,4-triazol-3-yl group, a 1,3,4-oxadiazol-2-yl group or a1,3,4-thiadiazol-2-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and a C1-C3haloalkyl group.

[9] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-benzothiazolyl group or a2-benzimidazolyl group, and the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a halogenatom, a cyano group, a C1-C3 alkyl group and a C1-C3 haloalkyl group.

[10] The carboxamide compound according to [1], wherein Q is a2-benzimidazolyl group optionally substituted with at least one groupselected from the group consisting of a halogen atom, a cyano group, aC1-C3 alkyl group and a C1-C3 haloalkyl group.

[11] The carboxamide compound according to any one of [1] to [10],wherein R³ is a hydrogen atom or a C1-C3 alkyl group.

[12] The carboxamide compound according to any one of [1] to [10],wherein R³ is a hydrogen atom or a halogen atom.

[13] A plant disease controlling agent comprising the carboxamidecompound as defined in any one of [1] to [12] as an active ingredient,and an inert carrier.

[14] A method of controlling a plant disease, comprising a step oftreating a plant or a soil where a plant grows with an effective amountof the carboxamide compound as defined in any one of [1] to [12].

[15] Use of the carboxamide compound as defined in any one of [1] to[12] for controlling a plant disease.

In the present invention, as groups represented by Q, R¹, R² and R³, thefollowing specific examples are mentioned.

The C1-C3 alkyl group represented by R¹ include a methyl group, an ethylgroup, a propyl group and an isopropyl group, and examples of the C2-C5alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl groupand a propoxymethyl group.

The C1-C3 alkyl group represented by R² include a methyl group, an ethylgroup, a propyl group and an isopropyl group.

Examples of the C3-C4 alkylene group in which R¹ and R² are bound toeach other at an end include a trimethylene group and a tetramethylenegroup.

The halogen atom represented by R³ include a fluorine atom, a chlorineatom, a bromine atom and an iodine atom.

The C1-C3 alkyl group represented by R³ include a methyl group, an ethylgroup, a propyl group and an isopropyl group.

Q represents a nitrogen-containing 5-membered heterocyclic groupoptionally fused with a benzene ring. The nitrogen-containing 5-memberedheterocyclic group optionally fused with a benzene ring may besubstituted with at least one group selected from the group consistingof a halogen atom (e.g., a fluorine atom or a chlorine atom), a cyanogroup, a C1-C3 alkyl group (e.g., a methyl group, an ethyl group or apropyl group) and a C1-C3 haloalkyl group (e.g., a trifluoromethylgroup), at the 5-membered ring part and/or benzene ring part. Examplesof the heterocyclic group represented by Q include the following groups.

A nitrogen-containing 5-membered heterocyclic group optionally fusedwith a benzene ring in which the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a halogenatom, a cyano group, a C1-C3 alkyl group and a C1-C3 haloalkyl group anda carbon atom adjacent to a nitrogen atom among ring constitutionalatoms and a nitrogen atom of NH in the formula (I) bind to each other.

A nitrogen-containing 5-membered heterocyclic group optionally fusedwith a benzene ring in which the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a halogenatom, a cyano group, a C1-C3 alkyl group and a C1-C3 haloalkyl group andthe heterocyclic group has one nitrogen atom, and at least one heteroatom selected from an oxygen atom, sulfur atom and nitrogen atom as aring constitutional atom.

A nitrogen-containing 5-membered heterocyclic group not fused with otherring in which the heterocyclic group may be substituted with at leastone group selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group.

A nitrogen-containing 5-membered heterocyclic group fused with a benzenering in which the heterocyclic group may be substituted with at leastone group selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group, on the5-membered ring and/or benzene ring.

A heterocyclic group represented by the formula (a-1) or the formula(a-2):

[wherein, Z¹ represents an oxygen atom, a sulfur atom or NA¹, Z²represents a nitrogen atom or CA² group, and Z³ represents a nitrogenatom or CA³ group,

A¹ represents a hydrogen atom or C1-C3 alkyl group (e.g., a methylgroup, an ethyl group or a propyl group), A² represents a hydrogen atom,halogen atom (e.g., a fluorine atom or a chlorine atom), a cyano group,a C1-C3 alkyl group (e.g., a methyl group, an ethyl group or a propylgroup) or a C1-C3 haloalkyl group (e.g., a trifluoromethyl group),

A³ represents a hydrogen atom, a halogen atom (e.g., a fluorine atom ora chlorine atom), a cyano group, a C1-C3 alkyl group (e.g., a methylgroup, an ethyl group or a propyl group) or a C1-C3 haloalkyl group(e.g., a trifluoromethyl group), or A² and A³ bind to each other at anend to represent a 1,3-butadiene-1,4-diyl group optionally substitutedwith a halogen atom, a cyano group, a C1-C3 alkyl group or a C1-C3haloalkyl group (e.g., 1,3-butadiene-1,4-diyl group,2-fluoro-1,3-butadiene-1,4-diyl group, 2-chloro-1,3-butadiene-1,4-diylgroup, 2-cyano-1,3-butadiene-1,4-diyl group,2-methyl-1,3-butadiene-1,4-diyl group,2-trifluoromethyl-1,3-butadiene-1,4-diyl group,1-fluoro-1,3-butadiene-1,4-diyl group, 1-chloro-1,3-butadiene-1,4-diylgroup and 1-methyl-1,3-butadiene-1,4-diyl group). Here, if Z¹ is NA¹ andA¹ is a hydrogen atom, then, Z² is a CA² group and Z³ is a CA³ group.

Z⁴ represents an oxygen atom, a sulfur atom or NA⁴, Z⁵ represents anitrogen atom or CA⁵, and Z⁶ represents a nitrogen atom or CA⁶,

A⁴ represents a hydrogen atom or C1-C3 alkyl group (e.g., a methylgroup, an ethyl group or a propyl group), A⁵ represents a hydrogen atomor C1-C3 alkyl group (e.g., a methyl group, an ethyl group or a propylgroup), and A⁶ represents a hydrogen atom or a C1-C3 alkyl group (e.g.,a methyl group, an ethyl group or a propyl group).].

A heterocyclic group which is a thiazolyl group, benzothiazolyl group,an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a1,2,4-oxadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,2,4-thiazolylgroup, a 1,3,4-oxadiazolyl group or a 1,3,4-thiadiazolyl group in whichthe heterocyclic group may be substituted with at least one groupselected from the group consisting of a halogen atom, a cyano group, aC1-C3 alkyl group and a C1-C3 haloalkyl group.

A heterocyclic group which is a 2-thiazolyl group, a 2-benzothiazolylgroup, a 2-imidazolyl group, a 2-benzimidazolyl group, a 3-pyrazolylgroup, a 1,2,4-oxadiazol-5-yl group, a 1,2,4-thiadiazol-5-yl group, a1,2,4-triazol-3-yl group, a 1,3,4-oxadiazol-2-yl group or a1,3,4-thiadiazol-2-yl group in which the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and a C1-C3haloalkyl group.

Specific examples of the heterocyclic group represented by Q includea2-imidazolyl group, a4-methyl-2-imidazolyl group, a4,5-dimethyl-2-imidazolyl group, a 4-chloro-2-imidazolyl group, a4-bromo-2-imidazolyl group, a 4,5-dicyano-2-imidazolyl group, a4-fluoro-2-imidazolyl group, a 4-cyano-2-imidazolyl group,

a 2-benzimidazolyl group, a 4-fluoro-2-benzimidazolyl group, a5-fluoro-2-benzimidazolyl group, a 4-chloro-2-benzimidazolyl group, a5-chloro-2-benzimidazolyl group, a 4-cyano-2-benzimidazolyl group, a5-cyano-2-benzimidazolyl group, a 4-methyl-2-benzimidazolyl group, a5-methyl-2-benzimidazolyl group, a 4-trifluoromethyl-2-benzimidazolylgroup, a 5-trifluoromethyl-2-benzimidazolyl group, a5,6-dimethyl-2-benzimidazolyl group, a 5,6-difluoro-2-benzimidazolylgroup, a 5,6-dichloro-2-benzimidazolyl group, a5-trifluoromethyl-2-benzimidazolyl group, a 5-cyano-2-benzimidazolylgroup,

a 2-thiazolyl group, a 4-methyl-2-thiazolyl group, a4,5-dimethyl-2-thiazolyl group, a 4-chloro-2-thiazolyl group, a4-bromo-2-thiazolyl group, a 4,5-dicyano-2-thiazolyl group, a4-fluoro-2-thiazolyl group, a 4-cyano-2-thiazolyl group,

a 2-benzothiazolyl group, a 4-fluoro-2-benzothiazolyl group, a5-fluoro-2-benzothiazolyl group, a 6-fluoro-2-benzothiazolyl group, a7-fluoro-2-benzothiazolyl group, a 4-chloro-2-benzothiazolyl group, a5-chloro-2-benzothiazolyl group, a 6-chloro-2-benzothiazolyl group, a7-chloro-2-benzothiazolyl group, a 4-methyl-2-benzothiazolyl group, a5-methyl-2-benzothiazolyl group, a 6-methyl-2-benzothiazolyl group, a7-methyl-2-benzothiazolyl group, a 5,6-dimethyl-2-benzothiazolyl group,a 5,6-difluoro-2-benzothiazolyl group, a 5,6-dichloro-2-benzothiazolylgroup, a 5-trifluoromethyl-2-benzothiazolyl group, a5-cyano-2-benzothiazolyl group,

a 1-methyl-3-pyrazolyl group, a 1,5-dimethyl-3-pyrazolyl group, a4-chloro-1-methyl-3-pyrazolyl group, a 1-ethyl-3-pyrazolyl group, a1-(2,2,2-trifluoroethyl)-3-pyrazolyl group, a 1,2,4-thiadiazol-5-ylgroup, a 3-methyl-1,2,4-thiadiazol-5-yl group, a3-trifluoromethyl-1,2,4-thiadiazol-5-yl group, a3-cyano-1,2,4-thiadiazol-5-yl group, a 1,3,4-thiadiazol-2-yl group, a5-methyl-1,3,4-thiadiazol-2-yl group, a5-trifluoromethyl-1,3,4-thiadiazol-2-yl group and a5-cyano-1,3,4-thiadiazol-2-yl group.

Embodiments of the present compound include, for example, the followingcompounds among the present compounds.

A carboxamide compound represented by the formula (I) in which Q is anitrogen-containing 5-membered heterocyclic group optionally fused witha benzene ring, the heterocyclic group may be substituted with at leastone group selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group, and theheterocyclic group has one nitrogen atom, and at least one hetero atomselected from an oxygen atom, a sulfur atom and a nitrogen atom as aring constitutional atom.

A carboxamide compound represented by the formula (I) in which Q is anitrogen-containing 5-membered heterocyclic group optionally fused witha benzene ring, the heterocyclic group may be substituted with at leastone group selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group, and a carbonatom adjacent to a nitrogen atom among ring constitutional atoms and anitrogen atom of NH in the formula (I) bind to each other.

A carboxamide compound represented by the formula (I) in which Q is anitrogen-containing 5-membered heterocyclic group not fused with otherring, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group;

A carboxamide compound represented by the formula (I) in which Q is anitrogen-containing 5-membered heterocyclic group fused with a benzenering, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a halogen atom, a cyanogroup, a C1-C3 alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which Q is aheterocyclic group represented by the formula (a-1) or the formula(a-2):

[wherein, Z¹ represents an oxygen atom, a sulfur atom or NA¹, Z²represents a nitrogen atom or CA² group, Z³ represents a nitrogen atomor CA³ group, A¹ represents a hydrogen atom or a C1-C3 alkyl group, A²represents a hydrogen atom, a halogen atom, cyano group, a C1-C3 alkylgroup or a C1-C3 haloalkyl group, A³ represents a hydrogen atom, ahalogen atom, a cyano group, a C1-C3 alkyl group or a C1-C3 haloalkylgroup, or A² and A³ bind to each other at an end to represent a1,3-butadiene-1,4-diyl group optionally substituted with a halogen atom,a cyano group, C1-C3 alkyl group or a C1-C3 haloalkyl group. Here, if Z¹is NA¹ and A¹ is a hydrogen atom, then, Z² is a CA² group and Z³ is aCA³ group.

Z⁴ represents an oxygen atom, a sulfur atom or NA⁴, Z⁵ represents anitrogen atom or CA⁵, and Z⁶ represents a nitrogen atom or CA⁶, A⁴represents a hydrogen atom or a C1-C3 alkyl group, A⁵ represents ahydrogen atom or a C1-C3 alkyl group, and A⁶ represents a hydrogen atomor a C1-C3 alkyl group.].

A carboxamide compound represented by the formula (I) in which Q is aheterocyclic group which is a thiazolyl group, a benzothiazolyl group,an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a1,2,4-oxadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,2,4-triazolylgroup, a 1,3,4-oxadiazolyl group or a 1,3,4-thiadiazolyl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which Q is aheterocyclic group which is a 2-thiazolyl group, a 2-benzothiazolylgroup, a 2-imidazolyl group, a 2-benzimidazolyl group, a 3-pyrazolylgroup, a 1,2,4-oxadiazol-5-yl group, a 1,2,4-thiadiazol-5-yl group, a1,2,4-triazol-3-yl group, a 1,3,4-oxadiazol-2-yl group or a1,3,4-thiadiazol-2-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and a C1-C3haloalkyl group.

A carboxamide compound represented by the formula (I) in which Q is aheterocyclic group which is a 2-thiazolyl group, a 2-imidazolyl group, a3-pyrazolyl group, a 1,2,4-oxadiazol-5-yl group, a 1,2,4-thiadiazol-5-ylgroup, a 1,2,4-triazol-3-yl group, a 1,3,4-oxadiazol-2-yl group or a1,3,4-thiadiazol-2-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and a C1-C3haloalkyl group.

A carboxamide compound represented by the formula (I) in which Q is aheterocyclic group which is a 2-benzothiazolyl group or a2-benzimidazolyl group, and the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a halogenatom, a cyano group, a C1-C3 alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which Q is a2-benzimidazolyl group optionally substituted with at least one groupselected from the group consisting of a halogen atom, a cyano group, aC1-C3 alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which Q is a2-imidazolyl group, a 4-methyl-2-imidazolyl group, a4,5-dimethyl-2-imidazolyl group, a 4-chloro-2-imidazolyl group, a4-bromo-2-imidazolyl group, a 4,5-dicyano-2-imidazolyl group, a4-fluoro-2-imidazolyl group or a 4-cyano-2-imidazolyl group.

A carboxamide compound represented by the formula (I) in which Q is a2-benzimidazolyl group, a 4-fluoro-2-benzimidazolyl group, a5-fluoro-2-benzimidazolyl group, a 4-chloro-2-benzimidazolyl group, a5-chloro-2-benzimidazolyl group, a 4-methyl-2-benzimidazolyl group, a5-methyl-2-benzimidazolyl group, a 5,6-dimethyl-2-benzimidazolyl group,a 5,6-difluoro-2-benzimidazolyl group, a 5,6-dichloro-2-benzimidazolylgroup, a 5-trifluoromethyl-2-benzimidazolyl group or a5-cyano-2-benzimidazolyl group.

A carboxamide compound represented by the formula (I) in which Q is a2-thiazolyl group, a 4-methyl-2-thiazolyl group, a4,5-dimethyl-2-thiazolyl group, a 4-chloro-2-thiazolyl group, a4-bromo-2-thiazolyl group, a 4,5-dicyano-2-thiazolyl group, a4-fluoro-2-thiazolyl group or a 4-cyano-2-thiazolyl group.

A carboxamide compound represented by the formula (I) in which Q is a2-benzothiazolyl group, a 4-fluoro-2-benzothiazolyl group, a5-fluoro-2-benzothiazolyl group, a 6-fluoro-2-benzothiazolyl group, a7-fluoro-2-benzothiazolyl group, a 4-chloro-2-benzothiazolyl group, a5-chloro-2-benzothiazolyl group, a 6-chloro-2-benzothiazolyl group, a7-chloro-2-benzothiazolyl group, a 4-methyl-2-benzothiazolyl group, a5-methyl-2-benzothiazolyl group, a 6-methyl-2-benzothiazolyl group, a7-methyl-2-benzothiazolyl group, a 5,6-dimethyl-2-benzothiazolyl group,a 5,6-difluoro-2-benzothiazolyl group, a 5,6-dichloro-2-benzothiazolylgroup, a 5-trifluoromethyl-2-benzothiazolyl group or a5-cyano-2-benzothiazolyl group.

A carboxamide compound represented by the formula (I) in which Q is a1,2,4-thiadiazol-5-yl group, a 3-methyl-1,2,4-thiadiazol-5-yl group, a3-trifluoromethyl-1,2,4-thiadiazol-5-yl group or a3-cyano-1,2,4-thiadiazol-5-yl group.

A carboxamide compound represented by the formula (I) in which Q is a1,3,4-thiadiazol-2-yl group, a 5-methyl-1,3,4-thiadiazol-2-yl group, a5-trifluoromethyl-1,3,4-thiadiazol-2-yl group or a5-cyano-1,3,4-thiadiazol-2-yl group.

A carboxamide compound represented by the formula (I) in which R² is ahydrogen atom and R³ is a hydrogen atom or a C1-C3 alkyl group.

A carboxamide compound represented by the formula (I) in which R² is amethyl group and R³ is a hydrogen atom or a C1-C3 alkyl group.

A carboxamide compound represented by the formula (I) in which R² is ahydrogen atom and R³ is a hydrogen atom or a C1-C3 alkyl group.

A carboxamide compound represented by the formula (I) in which R¹ is amethyl group, R² is a hydrogen atom, and R³ is a hydrogen atom or aC1-C3 alkyl group.

A carboxamide compound represented by the formula (I) in which R¹ is amethyl group, R² is a methyl group, and R³ is a hydrogen atom or a C1-C3alkyl group.

A carboxamide compound represented by the formula (I) in which R¹ is amethyl group, R² is a hydrogen atom, and R³ is a hydrogen atom or aC1-C3 alkyl group.

A carboxamide compound represented by the formula (I) in which R¹ and R²bind to each other at an end to form a trimethylene group, and R³ is ahydrogen atom or a C1-C3 alkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a nitrogen-containing5-membered heterocyclic group optionally fused with a benzene ring, theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group and the heterocyclic group hasone nitrogen atom, and at least one hetero atom selected from an oxygenatom, a sulfur atom and a nitrogen atom as a ring constitutional atom.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a nitrogen-containing5-membered heterocyclic group optionally fused with a benzene ring, theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group; and a carbon atom adjacent to anitrogen atom among ring constitutional atoms and a nitrogen atom of NHin the formula (I) bind to each other.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a nitrogen-containing5-membered heterocyclic group not fused with other ring, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a nitrogen-containing5-membered heterocyclic group fused with a benzene ring, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a heterocyclic grouprepresented by the formula (a-1) or the formula (a-2):

[wherein, Z¹ represents an oxygen atom, a sulfur atom or NA¹, Z²represents a nitrogen atom or CA² group, Z³ represents a nitrogen atomor CA³ group, A¹ represents a hydrogen atom or a C1-C3 alkyl group, A²represents a hydrogen atom, a halogen atom, cyano group, a C1-C3 alkylgroup or a C1-C3 haloalkyl group, A³ represents a hydrogen atom, ahalogen atom, a cyano group, a C1-C3 alkyl group or a C1-C3 haloalkylgroup, or A² and A³ may bind to each other at an end to represent a1,3-butadiene-1,4-diyl group optionally substituted with a halogen atom,a cyano group, a C1-C3 alkyl group or a C1-C3 haloalkyl group. Here, ifZ¹ is NA¹ and A¹ is a hydrogen atom, then, Z² is a CA² group and Z³ is aCA³ group.

Z⁴ represents an oxygen atom, sulfur atom or NA⁴, Z⁵ represents anitrogen atom or CA⁵, and Z⁶ represents a nitrogen atom or CA⁶, A⁴represents a hydrogen atom or a C1-C3 alkyl group, A⁵ represents ahydrogen atom or a C1-C3 alkyl group, and A⁶ represents a hydrogen atomor a C1-C3 alkyl group.].

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a heterocyclic group which isa thiazolyl group, a benzothiazolyl group, an imidazolyl group, abenzimidazolyl group, a pyrazolyl group, a 1,2,4-oxadiazolyl group, a1,2,4-thiadiazolyl group, a 1,2,4-triazolyl group, a 1,3,4-oxadiazolylgroup or a 1,3,4-thiadiazolyl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and a C1-C3haloalkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a heterocyclic group which isa 2-thiazolyl group, a 2-benzothiazolyl group, a 2-imidazolyl group, a2-benzimidazolyl group, a 3-pyrazolyl group, a 1,2,4-oxadiazol-5-ylgroup, a 1,2,4-thiadiazol-5-yl group, a 1,2,4-triazol-3-yl group, a1,3,4-oxadiazol-2-yl group or a 1,3,4-thiadiazol-2-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a heterocyclic group which isa 2-thiazolyl group, a 2-imidazolyl group, a 3-pyrazolyl group, a1,2,4-oxadiazol-5-yl group, a 1,2,4-thiadiazol-5-yl group, a1,2,4-triazol-3-yl group, a 1,3,4-oxadiazol-2-yl group or a1,3,4-thiadiazol-2-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a halogen atom, a cyano group, a C1-C3 alkyl group and a C1-C3haloalkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a heterocyclic group which isa 2-benzothiazolyl group or a 2-benzimidazolyl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a halogen atom, a cyano group, a C1-C3alkyl group and a C1-C3 haloalkyl group;

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a 2-benzimidazolyl groupoptionally substituted with at least one group selected from the groupconsisting of a halogen atom, a cyano group, a C1-C3 alkyl group and aC1-C3 haloalkyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a 2-imidazolyl group, a4-methyl-2-imidazolyl group, a 4,5-dimethyl-2-imidazolyl group, a4-chloro-2-imidazolyl group, a 4-bromo-2-imidazolyl group, a4,5-dicyano-2-imidazolyl group, a 4-fluoro-2-imidazolyl group or a4-cyano-2-imidazolyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a 2-benzimidazolyl group,a 4-fluoro-2-benzoimidazolyl group, a 5-fluoro-2-benzimidazolyl group, a4-chloro-2-benzimidazolyl group, a 5-chloro-2-benzimidazolyl group, a4-methyl-2-benzimidazolyl group, a 5-methyl-2-benzimidazolyl group, a5,6-dimethyl-2-benzimidazolyl group, a 5,6-difluoro-2-benzimidazolylgroup, a 5,6-dichloro-2-benzimidazolyl group, a5-trifluoromethyl-2-benzimidazolyl group or a 5-cyano-2-benzimidazolylgroup.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a 2-thiazolyl group, a4-methyl-2-thiazolyl group, a 4,5-dimethyl-2-thiazolyl group, a4-chloro-2-thiazolyl group, a 4-bromo-2-thiazolyl group, a4,5-dicyano-2-thiazolyl group, a 4-fluoro-2-thiazolyl group or a4-cyano-2-thiazolyl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, Q is a 2-benzothiazolyl group, a4-fluoro-2-benzothiazolyl group, a 5-fluoro-2-benzothiazolyl group, a6-fluoro-2-benzothiazolyl group, a 7-fluoro-2-benzothiazolyl group,4-chloro-2-benzothiazolyl group, a 5-chloro-2-benzothiazolyl group, a6-chloro-2-benzothiazolyl group, a 7-chloro-2-benzothiazolyl group, a4-methyl-2-benzothiazolyl group, a 5-methyl-2-benzothiazolyl group, a6-methyl-2-benzothiazolyl group, a 7-methyl-2-benzothiazolyl group, a5,6-dimethyl-2-benzothiazolyl group, a 5,6-difluoro-2-benzothiazolylgroup, a 5,6-dichloro-2-benzothiazolyl group, a5-trifluoromethyl-2-benzothiazolyl group or a 5-cyano-2-benzothiazolylgroup.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a 1,2,4-thiadiazol-5-ylgroup, a 3-methyl-1,2,4-thiadiazol-5-yl group, a3-trifluoromethyl-1,2,4-thiadiazol-5-yl group or a3-cyano-1,2,4-thiadiazol-5-yl group.

A carboxamide compound represented by the formula (I) in which R³ is ahydrogen atom or a C1-C3 alkyl group, and Q is a 1,3,4-thiadiazol-2-ylgroup, a 5-methyl-1,3,4-thiadiazol-2-yl group, a5-trifluoromethyl-1,3,4-thiadiazol-2-yl group or a5-cyano-1,3,4-thiadiazol-2-yl group.

A carboxamide compound represented by the formula (I) in which R² is ahydrogen atom and R³ is a hydrogen atom.

A carboxamide compound represented by the formula (I) in which R² is amethyl group and R³ is a hydrogen atom.

A carboxamide compound represented by the formula (I) in which R² is ahydrogen atom and R³ is a methyl group.

A carboxamide compound represented by the formula (I) in which R¹ is amethyl group, R² is a hydrogen atom, and R³ is a hydrogen atom.

A carboxamide compound represented by the formula (I) in which R¹ is amethyl group, R² is a methyl group, and R³ is a hydrogen atom.

A carboxamide compound represented by the formula (I) in which R¹ is amethyl group, R² is a hydrogen atom, and R³ is a methyl group.

A carboxamide compound represented by the formula (I) in which R¹ and R²bind to each other at an end to form a trimethylene group, and R³ is ahydrogen atom.

A carboxamide compound represented by the formula (I-100):

(wherein, R¹ represents a C1-C3 alkyl group or C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group, or R¹ and R² bindto each other at an end to represent a C3-C4 alkylene group, R³represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group, R¹⁰⁰represents a halogen atom, a cyano group, a C1-C3 alkyl group or a C1-C3haloalkyl group, and n represents an integer of 0 to 4).

A carboxamide compound represented by the formula (I-101):

(wherein, R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkylgroup, R² represents a hydrogen atom or a C1-C3 alkyl group, or R¹ andR² bind to each other at an end to represent a C3-C4 alkylene group, R³represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group, R¹⁰¹represents a halogen atom, a cyano group, a C1-C3 alkyl group or a C1-C3haloalkyl group, and n represents an integer of 0 to 2).

Next, a process for preparing the present compound will be explained.The present compound can be prepared, for example, according to thefollowing (Process A), (Process B) and (Process C).

In the following (Process A), (Process B), (Process C), and ReferenceProcess, if necessary, a protecting group for protecting a particularfunctional group may be used, and the protecting group can bedeprotected under the suitable condition.

(Process A)

The present compound can be prepared by reacting a compound representedby the formula (II) and a compound represented by the formula (III).

[wherein Q represents a nitrogen-containing 6-membered aromaticheterocyclic group optionally fused with a benzene ring, one of ringconstitutional atoms of the heterocyclic group is a nitrogen atom, andthe heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a halogen atom, a cyano group anda nitro group,R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group, or R¹ and R² arebound to each other at an end to represent a C3-C4 alkylene group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,andR⁴ represents a C1-C10 alkyl group.]

The reaction is performed usually in the presence of a solvent. Ifnecessary, the reaction may be performed while a C1-C10 alcohol producedaccompanying with progression of the reaction is removed by adsorption,distillation or azeotropy or the like.

Examples of the solvent to be used in the reaction include halogenatedaromatic hydrocarbons such as chlorobenzene, bromobenzene and the like,aromatic hydrocarbons such as toluene, xylene and the like, acid amidessuch as N,N-dimethylformamide and the like, and a mixture thereof.

At the reaction, the compound represented by the formula (II) is usuallyused at a ratio of 0.1 to 5 moles per 1 mole of the compound representedby the formula (III).

A reaction temperature in the reaction is usually in a range of 80 to180° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the present compound represented bythe formula (I) can be isolated, for example, by performing thefollowing post-treatment procedure. The reaction mixture is cooled toroom temperature, the resulting solid is collected by filtration, andthe solid is washed with an organic solvent and dried;

the reaction mixture is concentrated under reduced pressure, and theresulting solid is further washed with an organic solvent and dried.

The isolated present compound represented by the formula (I) may also befurther purified by a procedure such as chromatography,recrystallization and the like.

(Process B)

The present compound can be prepared by reacting a compound representedby the formula (XIII) and a compound represented by the formula (III)using carbonyldiimidazole.

[wherein R¹, R², R³ and Q are as defined above.]

The reaction is performed usually in the presence of a solvent. Examplesof the solvent used in the reaction include nitriles such asacetonitrile, propionitrile and the like, ethers such as diethyl ether,t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like,aromatic hydrocarbons such as toluene, xylene and the like, acid amidessuch as N,N-dimethylformamide and the like, and a mixture thereof.

At the reaction, the compound represented by the formula (III) isusually used at a ratio of 0.1 to 5 moles per 1 mole of the compoundrepresented by the formula (XIII). Carbonyldiimidazole is usually usedat a ratio of 0.1 to 5 moles per 1 mole of the compound represented bythe formula (XIII).

A reaction temperature in the reaction is usually in a range of −10 to150° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the present compound represented bythe formula (I) can be isolated by performing a post-treatment proceduresuch as the resulting solid being collected by filtration, washing thesolid with an organic solvent, drying it and so on. The isolated presentcompound represented by the formula (I) may also be further purified bya procedure such as chromatography, recrystallization and the like.

(Process C)

The present compound can be prepared by reacting a compound representedby the formula (XIII) and a compound represented by the formula (XV) inthe presence of alkaline earth metal triflate such as magnesiumtriflate, calcium triflate and the like.

[wherein R¹, R², R³ and Q are as defined above.]

The reaction is performed usually in the presence of a solvent. Examplesof the solvent used in the reaction include aromatic hydrocarbons suchas toluene, xylene and the like.

At the reaction, the compound represented by the formula (XV) is usuallyused at a ratio of 1 mole per 1 mole of the compound represented by theformula (XIII), and the alkaline earth metal triflate is usually used ata ratio of 0.01 to 0.1 moles per 1 mole of the compound represented bythe formula (XIII).

A reaction temperature in the reaction is usually in a range of 100 to150° C. and the reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (I) can be isolated by performing a post-treatment proceduresuch as the reaction mixture being cooled, the resulting solid beingcollected by filtration, washing the solid with an organic solvent,drying it and so on. The isolated compound represented by the formula(I) may also be further purified by a procedure such as chromatography,recrystallization and the like.

The compound represented by the formula (XV) can be prepared from acompound represented by the formula (XVI):OCN-Q  (XVI)and 3,5-dimethylimidazole.

Next, a process for preparing an intermediate for preparing the presentcompound will be explained as Reference Process.

(Reference Process 1)

A compound represented by the formula (II-1) among the compoundsrepresented by the formula (II) can be prepared from a compoundrepresented by the formula (IV) according to the following scheme.

[wherein Q is as defined, above, R¹¹ represents a C1-C3 alkyl group or aC2-C5 alkoxyalkyl group, R²¹ represents a hydrogen atom or a C1-C3 alkylgroup, R³¹ represents a hydrogen atom or a C1-C3 alkyl group, and R⁴represents a C1-C10 alkyl group]Step (1-1)

A compound represented by the formula (V-1) can be prepared by reactinga compound represented by the formula (IV) with an azide compound (e.g.sodium azide, and trimethylsilyl azide), and further reacting theresulting product with an alcohol compound (e.g. methanol, and ethanol).

The reaction is performed usually in the presence of a solvent. Examplesof the solvent used in the reaction include halogenated hydrocarbonssuch as chloroform, carbon tetrachloride and the like, halogenatedaromatic hydrocarbons such as chlorobenzene, bromobenzene and the like,aromatic hydrocarbons such as toluene, xylene and the like, acid amidessuch as N,N-dimethylformamide and the like and a mixture thereof.

At the reaction, the azide compound is usually used at a ratio of 1 to 5moles per 1 mole of the compound represented by the formula (IV), andthe alcohol compound is usually used at a ratio of 1 mole per 1 mole ofthe azide compound.

When the compound represented by the formula (IV) is reacted with theazide compound, a reaction temperature is usually in a range of −20 to100° C., and a reaction time is usually in a range of 0.1 to 24 hours.When the resulting product is reacted with the alcohol compound, areaction temperature is usually in a range of −20 to 10° C., and areaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (V-1) can be isolated by performing a post-treatment proceduresuch as a solid produced in the reaction mixture being collected byfiltration, washing the solid with an organic solvent, drying it and soon. The isolated compound represented by the formula (V-1) can befurther purified by a procedure such as chromatography,recrystallization and the like.

Alternatively, the compound represented by the formula (V-1) can be alsoprepared by the method shown in Tetrahedron Letters No. 4, pp. 243-246,1976.

Step (1-2)

A compound represented by the formula (VI-1) can be prepared by reactinga compound represented by the formula (V-1) with a compound representedby the formula (X):R¹¹—X  (X)[wherein R¹¹ is as defined above, and X represents a leaving group suchas a halogen atom (e.g. chlorine atom, bromine atom and iodine atom), asulfonyloxy group (e.g. methanesulfonyloxy group, methoxysulfonyloxygroup, and p-toluenesulfonyloxy group) and the like] in the presence ofa base.

The reaction is usually performed in the presence of a solvent. Examplesof the solvent used in the reaction include ketones such as acetone,ethyl methyl ketone and the like, halogenated aromatic hydrocarbons suchas chlorobenzene, bromobenzene and the like, aromatic hydrocarbons suchas toluene, xylene and the like, acid amides such asN,N-dimethylformamide and the like, ethers such as tetrahydrofuran,1,4-dioxane and the like, nitriles such as acetonitrile and the like,and a mixture thereof.

Examples of the compound represented by the formula (X) which is used inthe reaction include methyl iodide, methyl bromide, dimethyl sulfate,ethyl iodide, propyl iodide, and chloromethyl ethyl ether.

Examples of the base used in the reaction include carbonates such aspotassium carbonate, cesium carbonate and the like, and alkali metalhydrides such as sodium hydride, potassium hydride and the like.

At the reaction, the compound represented by the formula (X) is usuallyused at a ratio of 1 to 5 moles per 1 mole of the compound representedby the formula (VI-1), and the base is usually used at a ratio of 1 to 5moles per 1 mole of the compound represented by the formula (VI-1).

A reaction temperature in the reaction is usually in a range of −20 to150° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (VI-1) can be isolated by performing the followingpost-treatment procedure.

The reaction mixture is cooled to room temperature and filtered, thefiltrate is concentrated under reduced pressure, and the resulting solidis washed with an organic solvent and dried;

water is added to the reaction mixture, this is extracted with anorganic solvent and the organic layer is concentrated.

The isolated compound represented by the formula (VI-1) may also befurther purified by a procedure such as chromatography,recrystallization and the like.

Step (1-3)

A compound represented by the formula (II-1) can be prepared by reactinga compound represented by the formula (VI-1) with dialkyl malonaterepresented by the formula:CH₂(COOR⁴)₂(wherein R⁴ is as defined above)in the presence of a base.

The reaction is usually performed in the presence of a solvent. Examplesof the solvent used in the reaction include ethers such astetrahydrofuran, 1,4-dioxane and the like, halogenated aromatichydrocarbons such as chlorobenzene, bromobenzene and the like, aromatichydrocarbons such as toluene, xylene and the like, acid amides such asN,N-dimethylformamide and the like, and a mixture thereof.

Examples of the dialkyl malonate represented by the formula CH₂ (COOR⁴)₂used in the reaction include dimethyl malonate and diethyl malonate.

Examples of the base used in reaction include: metal alkoxidesrepresented by the formula:NaOR⁴(wherein R⁴ is as defined above) andalkali metal hydrides such as sodium hydride, potassium hydride and thelike.

At the reaction, dialkyl malonate is usually used at a ratio of 1 to 5moles per 1 mole of the compound represented by the formula (VI-1), andthe base is usually used at a ratio of 1 to 5 moles per 1 mole of thecompound represented by the formula (VI-1).

A reaction temperature in the reaction is usually in a range of −10 to150° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (II-1) can be isolated by performing a post-treatment proceduresuch as the reaction mixture being cooled to room temperature, addingacidic water such as dilute hydrochloric acid and the like to thereaction mixture to make the aqueous layer acidic, extracting this withan organic solvent, drying and concentrating the organic layer, and soon. The isolated compound represented by the formula (II-1) may also befurther purified by a procedure such as chromatography,recrystallization and the like.

In addition, a compound represented by the formula (II-2) among thecompound represented by the formula (II) can be prepared, for example,according to the following scheme:

[wherein, Q, R¹¹ and R⁴ are as defined above, R²² represents a C1-C3alkyl group, R³² represents a halogen atom, and R⁴ represents a C1-C10alkyl group.]Step (1′-1)

A compound represented by the formula (V-2) can be prepared according tothe method described in Tetrahedron Letters No. 4, pp 243-246, 1976.

A step (1′-2) and a step (1′-3) are performed as in the step (1-2) andthe step (1-3).

(Reference Process 2)

The compound represented by the formula (II) can also be preparedaccording to the following scheme:

[wherein R¹, R², R³, R⁴ and Q are as defined above.]Step (2-1)

The compound represented by the formula (II) can be prepared by reactinga compound represented by the formula (VII) with a compound representedby the formula (VIII).

The reaction can be performed usually in the absence of a solvent.Alternatively, the reaction may be performed in the presence of asolvent while an alcohol compound produced accompanying a reaction isremoved by azeotropy and the like. Examples of the solvent used in thereaction include halogenated aromatic hydrocarbons such aschlorobenzene, bromobenzene and the like, aromatic hydrocarbons such astoluene, xylene and the like, acid amides such as N,N-dimethylformamideand the like, and a mixture thereof.

At the reaction, the compound represented by the formula (VIII) isusually used at a ratio of 1 to 50 moles per 1 mole of the compoundrepresented by the formula (VII).

A reaction temperature in the reaction is usually in a range of 100 to250° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (II) can be isolated, for example, by performing the followingpost-treatment procedure.

The reaction mixture is cooled to room temperature, the resulting solidis filtered, and the solid is washed with an organic solvent and dried;

after the reaction mixture is cooled to room temperature, water is addedto the reaction mixture, this is extracted with an organic solvent, andthe organic layer is concentrated.

The isolated compound represented by the formula (II) may also befurther purified by a procedure such as chromatography,recrystallization and the like.

(Reference Process 3)

Among the compound represented by the formula (XIII), a compoundrepresented by the formula (XIII-1) can be prepared from a compoundrepresented by the formula (XVII) according to the following scheme:

[wherein R¹³ represents a C1-C3 alkyl group.](Step 3-1)

A compound represented by the formula (XVIII) can be prepared byreacting a compound represented by the formula (XVII) with diketenerepresented by the formula (XIX) in the presence of tertiary amine orpyridines (first stage), and reacting the resulting product with acompound represented by the formula (XX) (second stage).

Each reaction is usually performed in the presence of a solvent.Examples of the solvent used in the reaction include nitriles such asacetonitrile, propionitrile and the like, ethers such as diethyl ether,t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like,halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzeneand the like, aromatic hydrocarbons such as toluene, xylene and thelike, and a mixture thereof.

In the reaction at the first stage, diketene represented by the formula(XIX) is usually used at a ratio of 1 mole per 1 mole of the compoundrepresented by the formula (XVII).

In the reaction at the first stage, examples of the tertiary amine usedinclude triethylamine and tri-n-propylamine; examples of pyridinesinclude pyridine and 4-dimethylaminopyridine. In the reaction at thefirst stage, tertiary amine or pyridines is usually used at a ratio of 1mole per 1 mole of the compound represented by the formula (XVII).

A reaction temperature at the first stage is usually in a range of 0 to40° C., and a reaction time is usually in a range of 0.1 to 24 hours.

The reaction mixture obtained by the reaction at the first stage isusually used as it is in the reaction at the second stage.

The reaction at the second stage is usually performed by mixing thereaction mixture obtained at the first stage and a compound representedby the formula (XX).

In the reaction at the second stage, the compound represented by theformula (XX) is usually used at a ratio of 2 mole per 1 mole of thecompound represented by the formula (XVII).

A reaction temperature in the reaction at the second stage is usually ina range of 0 to 40° C., and a reaction time is usually in a range of 0.1to 24 hours.

After completion of the reaction at the second stage, the compoundrepresented by the formula (XVIII) can be isolated by performing apost-treatment procedure such as by adding acid (e.g. dilutehydrochloric acid, dilute sulfuric acid) to the reaction mixture,collecting the resulting crystal by filtration, drying it and so on. Theisolated compound represented by the formula (XVIII) may also be furtherpurified by a procedure such as chromatography, recrystallization andthe like.

(Step 3-2)

A compound represented by the formula (XIII-1) can be prepared byretaining a compound represented by the formula (XVIII) at 40 to 120° C.for 0.1 to 24 hours.

The procedure is usually performed in the presence of a solvent.Examples of the solvent used in the procedure include nitriles such asacetonitrile, propionitrile and the like, ethers such as t-butyl methylether, tetrahydrofuran, 1,4-dioxane and the like, halogenated aromatichydrocarbons such as chlorobenzene, bromobenzene and the like, aromatichydrocarbons such as toluene, xylene and the like, and a mixturethereof.

After disappearance of the compound represented by the formula (XVIII)is confirmed by an analysis means such as thin layer chromatography andthe like, the compound represented by the formula (XIII-1) can beisolated by performing a post-treatment procedure such as addition ofthe resulting mixture to water, extraction with an organic solvent,concentration of an organic layer and the like. The isolated compoundrepresented by the formula (XIII-1) may also be further purified by aprocedure such as chromatography, recrystallization and the like.

(Reference Process 4)

Among the compound represented by the formula (XIII), a compoundrepresented by the formula (XIII-2) can be prepared by reacting acompound represented by the formula (XVIII) with a halogenating agent at−10 to 30° C. (first stage) and retaining the resulting product at 40 to120° C. for 0.1 to 24 hours (second stage):

[wherein R³⁴ represents a halogen atom, and R¹³ is as defined above.]

The reaction at the first stage is usually performed in the presence ofa solvent. Examples of the solvent used in the reaction include nitrilessuch as acetonitrile, propionitrile and the like, ethers such as diethylether, t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like,halogenated aromatic hydrocarbons such as chlorobenzene and bromobenzeneand the like, aromatic hydrocarbons such as toluene, xylene and thelike, and a mixture thereof.

Examples of the halogenating agent used in the reaction at the firststage include N-fruoropyridinium salt such asN,N′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) and the like, andN-halogenosuccinimides such as N-chlorosuccinimide, N-bromosuccinimide,N-iodosuccinimide and the like.

At the reaction, the halogenating agent is usually used at a ratio of0.5 to 2 moles per 1 mole of the compound represented by the formula(XVIII).

A reaction temperature at the first stage is usually in a range of −10to 30° C., and a reaction time is usually in a range of 0.1 to 5 hours.

The reaction mixture obtained in the reaction at the first stage can beusually used as it is in a procedure at the second stage.

The procedure at the second stage is usually performed by retaining thereaction mixture obtained in the first stage at 40 to 120° C.

Thereafter, the compound represented by the formula (XIII-2) can beisolated by performing a post-treatment procedure, such as addition ofthe reaction mixture to water, extraction with an organic solvent,concentration of the organic layer and the like. The isolated compoundrepresented by the formula (XIII-2) may also be further purified by aprocedure such as chromatography, recrystallization and the like.

A compound represented by the formula (III) can be purchasedcommercially or prepared according to the method described in, forexample, Indian Journal of Chemistry, Section B: Organic ChemistryIncluding Medicinal Chemistry (1998), 37B(1), 84 p, Bioorganic &Medicinal Chemistry Letters (2002), 12(16), 2221-2224 p, JP-B No.52-009736, Journal of Organic Chemistry (1994), 59(24), 7299-7305 p,Phosphorus, Sulfur and Silicon and the Related Elements (2002), 177(11),2651-2659 p, Bioorganic & Medicinal Chemistry (2001), 9(12), 3231-3241,Chemische Berichte (1960), 93, 2190-2097 p, “The Chemistry ofHeterocyclic Compounds” (John Wiley & Sons, Inc.) and so on.

A compound represented by the formula (IV), a compound represented bythe formula (VII), a compound represented by the formula (VIII), acompound represented by the formula (X) and dialkyl malonate can bepurchased commercially or prepared according to the known methods.

Examples of a plant disease which can be controlled by the presentcompound include the following diseases:

Pyricularia oryzae and Cochliobolus miyabeanus and Rhizoctonia solani ofrice;

Erysiphe graminis, Gibberella zeae, Fusarium graminearum, Fusariumculmorum, F. avenaceum, Microdochium nivale, Puccinia striiformis, P.graminis, P. recondita, P. hordei, Typhula sp., Micronectriella nivalis,Ustilago tritici, U. nuda, Tilletia caries, Pseudocercosporellaherpotrichoides, Rhynchosporium secalis, Septoria tritici, Leptosphaerianodorum and Gaeumanomyces graminis, of wheat and barley;Diaporthe citri, Elsinoe fawcetti, Penicillium digitatum and P. italicumof citrus;Sclerotinia mali, Valsa mali, Podosphaera leucotricha, Alternaria maliand Venturia inaequalis of apple;Venturia nashicola, V. pirina, Alternaria kikuchiana and Gymnosporangiumharaeanum of pear;Sclerotinia cinerea, Cladosporium carpophilum and Phomopsis sp. ofpeach; Elsinoe ampelina, Glomerella cingulata, Uncinula necator,Phakopsora ampelopsidis, Guignardia bidwellii and Plasmopara viticola,of grape;Gloeosporium kaki, Cercospora kaki and Mycosphaerella nawae of Japanesepersimmon;Colletotrichum lagenarium, Sphaerotheca fuliginea, Mycosphaerellamelonis, Fusarium oxysporum, Pseudoperonospora cubensis, Phytophthorasp. and Pythium sp. of gourd;Alternaria solani, Cladosporium fulvum and Phytophthora infestans oftomato;Phomopsis vexans and Erysiphe cichoracearum, of eggplant;Alternaria japonica and Cercosporella brassicae of Cruciferaevegetables;Puccinia allii of leek; Cercospora kikuchii, Elsinoe glycines, Diaporthephaseolorum var. sojae and Phakospora pachrhizii of soybean;Colletotrichum lindemthianum of kidney bean; Cercospora personata andCercospora arachidicola of peanut; Erysiphe pisi of pea; Alternariasolani and Phytophthora infestans of potato; Sphaerotheca humuli ofstrawberry; Exobasidium reticulatum and Elsinoe leucospila of tea;Alternaria longipes, Erysiphe cichoracearum, Colletotrichum tabacum,Peronospora tabacina and Phytophthora nicotianae of tobacco; Cercosporabeticola of sugar beet; Diplocarpon rosae and Sphaerotheca pannosa ofrose; Septoria chrysanthemi-indici and Puccinia horiana ofchrysanthemum; Botrytis cinerea and Sclerotinia sclerotiorum of variouscrops; Sclerotinia homeocarpaa and Rhizoctonia solani of lawn.

The plant disease controlling agent of the present invention may be thepresent compound itself, but usually, the agent contains the presentcompound, and an inert carrier such as a solid carrier, a liquid carrierand the like, and is formulated in preparations by further mixing asurfactant, and other adjuvant for preparations. Examples of such thepreparations includes emulsifiable concentrates, wettable powders, waterdispersible granule, emulsion preparations, flowable preparations,dusts, and granules. These preparations contain the present compound asan active ingredient usually at 0.1 to 90% in terms of ratio by weight.

Examples of the solid carrier used upon formulating the preparationsinclude fine powders and particles of minerals such as kaolin clay,attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite,talc, diatomaceous earth, calcite and the like, natural organics such ascorncob powders, walnut shell flour and the like, synthetic organicssuch as urea and the like, salts such as calcium carbonate, ammoniumsulfate and the like, synthetic inorganic substances such as synthetichydrous silicon oxide and the like, and the examples of the liquidcarrier include aromatic hydrocarbons such as xylene, alkylbenzene,methylnaphthalene and the like, alcohols such as 2-propanol, ethyleneglycol, propylene glycol, ethylene glycol monomethyl ether and the like,ketones such as acetone, cyclohexanone, isophorone and the like,vegetable oils such as soybean oil, cottonseed oil and the like,aliphatic hydrocarbons, esters, dimethyl sulfoxide, acetonitrile, andwater.

Examples of the surfactant includes anionic surfactants such asalkylsulfate ester salt, alkylarylsulfonate salt, dialkylsulfosuccinatesalt, polyoxyethylene alkyl aryl ether phosphate ester salt,ligninsulfonate salt, naphathalene sulfonate formaldehyde polycondensateand the like, and noinic surfactants such as polyoxyethylene alkyl arylether, polyoxyethylene alkyl polyoxypropylene block copolymer, sorbitanfatty acid ester and the like.

Examples of other adjuvant for preparations include water-solublepolymers such as polyvinyl alcohol, polyvinylpyrrolidone and the like,polysaccarides such as gum arabic, alginic acid and a salt thereof, CMC(carboxymethylcellulose), xanthan gum and the like, inorganic substancessuch as aluminum magnesium silicate, alumina sol and the like,preservative, coloring agent, and stabilizers such as PAP (acidicisopropyl phosphate), BHT and the like.

The plant disease controlling agent of the present invention is used,for example, for protecting a plant against a plant disease by foliagetreatment of the plant, or is used for protecting a plant growing on asoil against a plant disease by treating the soil. When the plantdisease controlling agent of the present invention is used byfoliage-treating a plant, or when the agent is used by treating a soil,the amount of treatment varies depending on a kind of a crop which is aplant to be controlled, a kind of a disease to be controlled, aninfestation level of a disease to be controlled, a preparation form, atreating term, weather condition and the like, and the amount in termsof the present compound per 10000 m² is usually 1 to 5000 g, preferably5 to 1000 g.

In the case of emulsifiable concentrates, wettable powders, flowablepreparations and the like, a plant is usually treated by diluting theagent with water, followed by spraying. A concentration of the presentcompound is usually in a range of 0.0001 to 3% by weight, preferably ina range of 0.0005 to 1% by weight. In the case of dusts, granules andthe like, a plant is treated with the agent without dilution.

Alternatively, the plant disease controlling agent of the presentinvention may be used by a treating method such as seed disinfection.Examples of the method of disinfecting a seed include a method ofimmersing a plant seed in a plant disease controlling agent of thepresent invention which has been prepared so that a concentration of thepresent compound in adjusted to 1 to 1000 ppm, a method of spraying orapplying the plant disease controlling agent of the present inventionhaving a concentration of the present compound 1 to 1000 ppm on plantseeds, and a method of coating plant seeds with the plant diseasecontrolling agent of the present invention which has been formulatedinto powders.

The plant disease controlling method of the present invention is usuallyperformed by treating a plant which is expected to develop a disease ora soil where the plant grows, and/or treating a plant which is confirmedto have developed a disease or a soil where the plant grows with aneffective amount of the plant disease controlling agent of the presentinvention.

The plant disease controlling agent of the present invention is usuallyused as a plant disease controlling agent for horticulture, i.e., aplant disease controlling agent for controlling a plant disease inplowed field, paddy, orchard, tea garden, meadow, lawn and so on.

The plant disease controlling agent of the present invention may be used(mixed or combined) in conjunction with other fungicides, insecticides,acaricides, nematicides, herbicides, plant growth controlling agentsand/or fertilizers.

Examples of an active ingredient of such other fungicides includechlorothalonil, fluazinam, dichlofluanid, fosetyl-Al, cyclic imidoderivatives (captan, captafol, folpet etc.), dithiocarbamate derivatives(maneb, mancozeb, thiram, ziram, zineb, propineb etc.), inorganic ororganic copper derivatives (basic copper sulfate, copper oxychloride,copper hydroxide, oxine-copper etc.), acylalanine derivatives(metalaxyl, furalaxyl, ofurace, cyprofuram, benalaxyl, oxadixyl etc.),strobilurin compounds (kresoxim-methyl, azoxystrobin, trifloxystrobin,picoxystrobin, pyraciostrobin, dimoxystrobin, fluoxastrobin,metominostrobin etc.), anilinopyrimidine derivatives (cyprodinil,pyrimethanil, mepanipyrim etc.), phenylpyrrole derivatives (fenpiclonil,fludioxonil etc.), imide derivatives (procymidone, iprodione,vincrozolin etc.), benzimidazole derivatives (carbendazim, benomyl,thiabendazol, thiophanate-methyl etc.), amine derivatives(fenpropimorph, tridemorph, fenpropidin, spiroxamine etc.), azolederivatives (propiconazole, triadimenol, prochloraz, penconazole,tebuconazole, flusilazole, diniconazole, bromuconazole, epoxiconazole,difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole,myclobutanil, fenbuconazole, hexaconazole, fluquinconazole,triticonazole, bitertanol, imazalil, flutriafol etc.), cymoxanil,dimethomorph, famoxadone, fenamidone, iprovalicarb, benthiavalicarb,cyazofamid, picobenzamid, mandipropamide, zoxamide, ethaboxam, boscalid,pyribencarb, fluopicolide, fenhexamid, quinoxyfen, proquinazid,diethofencarb, acibenzolar-S-methyl, guazatine and penthiopyrad.

Specific examples of the present compound include the followingcompounds.

Carboxamide compounds represented by the following formulae (i) to(xxviii):

In the formulae (i) to (xxviii), Q represents any one of the followinggroups.

2-imidazolyl group, 4-methyl-2-imidazolyl group,4,5-dimethyl-2-imidazolyl group, 4-chloro-2-imidazolyl group,4-bromo-2-imidazolyl group, 4,5-dicyano-2-imidazolyl group,4-fluoro-2-imidazolyl group, 4-cyano-2-imidazolyl group,

2-benzimidazolyl group, 4-fluoro-2-benzimidazolyl group,5-fluoro-2-benzimidazolyl group, 4-chloro-2-benzimidazolyl group,5-chloro-2-benzimidazolyl group, 4-cyano-2-benzimidazolyl group,5-cyano-2-benzimidazolyl group, 4-methyl-2-benzimidazolyl group,5-methyl-2-benzimidazolyl group, 4-trifluoromethyl-2-benzimidazolylgroup, 5-trifluoromethyl-2-benzimidazolyl group,5,6-dimethyl-2-benzimidazolyl group, 5,6-difluoro-2-benzimidazolylgroup, 5,6-dichloro-2-benzimidazolyl group,5-trifluoromethyl-2-benzimidazolyl group, 5-cyano-2-benzimidazolylgroup,

2-thiazolyl group, 4-methyl-2-thiazolyl group, 4,5-dimethyl-2-thiazolylgroup, 4-chloro-2-thiazolyl group, 4-bromo-2-thiazolyl group,4,5-dicyano-2-thiazolyl group, 4-fluoro-2-thiazolyl group,4-cyano-2-thiazolyl group,

2-benzothiazolyl group, 4-fluoro-2-benzothiazolyl group,5-fluoro-2-benzothiazolyl group, 6-fluoro-2-benzothiazolyl group,7-fluoro-2-benzothiazolyl group, 4-chloro-2-benzothiazolyl group,5-chloro-2-benzothiazolyl group, 6-chloro-2-benzothiazolyl group,7-chloro-2-benzothiazolyl group, 4-methyl-2-benzothiazolyl group,5-methyl-2-benzothiazolyl group, 6-methyl-2-benzothiazolyl group,7-methyl-2-benzothiazolyl group, 5,6-dimethyl-2-benzothiazolyl group,5,6-difluoro-2-benzothiazolyl group, 5,6-dichloro-2-benzothiazolylgroup, 5-trifluoromethyl-2-benzothiazolyl group,5-cyano-2-benzothiazolyl group,

3-pyrazolyl group, 1-methyl-3-pyrazolyl group, 1,5-dimethyl-3-pyrazolylgroup, 4-chloro-1-methyl-3-pyrazolyl group, 1-ethyl-3-pyrazolyl group,1-(2,2,2-trifluoroethyl)-3-pyrazolyl group, 1,2,4-thiadiazol-5-yl group,3-methyl-1,2,4-thiadiazol-5-yl group,3-trifluoromethyl-1,2,4-thiadiazol-5-yl group,3-cyano-1,2,4-thiadiazol-5-yl group, 1,3,4-thiadiazol-2-yl group,5-methyl-1,3,4-thiadiazol-2-yl group,5-trifluoromethyl-1,3,4-thiadiazol-2-yl group and5-cyano-1,3,4-thiadiazol-2-yl group.

Embodiments of intermediates of the present compound include, forexample, the following compounds.

A compound represented by the formula (II) in which R¹ is a C1-C3 alkylgroup or C2-C5 alkoxyalkyl group, R² is a hydrogen atom or C1-C3 alkylgroup, and R³ is a hydrogen atom, halogen atom or C1-C3 alkyl group.

A compound represented by the formula (II) in which R¹ and R² bind toeach other at an end to form a C3-C4 alkylene group, and R³ is ahydrogen atom, halogen atom or C1-C3 alkyl group.

A compound represented by the formula (II) in which R¹ is a C1-C3 alkylgroup, R² is a hydrogen atom or C1-C3 alkyl group, and R³ is a hydrogenatom or C1-C3 alkyl group.

A compound represented by the formula (II) in which R¹ is a C1-C3 alkylgroup, R² is a hydrogen atom or C1-C3 alkyl group, and R³ is a halogenatom.

A compound represented by the formula (II) in which R¹ is a C1-C3 alkylgroup, R² is a hydrogen atom or C1-C3 alkyl group, and R³ is a fluorineatom.

A compound represented by the formula (II) in which R¹ is a C1-C3 alkylgroup, R² is a C1-C3 alkyl group, and R³ is a fluorine atom.

A compound represented by the formula (II) in which R¹ is a C1-C3 alkylgroup, R² is a methyl group, and R³ is a fluorine atom.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group or C2-C5 alkoxyalkyl group, R² is a hydrogen atom or C1-C3alkyl group, and R³ is a hydrogen atom, halogen atom or C1-C3 alkylgroup.

A compound represented by the formula (XIII) in which R¹ and R² bind toeach other at an end to form a C3-C4 alkylene group, and R³ is ahydrogen atom, halogen atom or C1-C3 alkyl group.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group, R² is a hydrogen atom or C1-C3 alkyl group, and R³ is ahydrogen atom or C1-C3 alkyl group.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group, R² is a hydrogen atom or C1-C3 alkyl group, and R³ is ahalogen atom.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group, R² is a hydrogen atom or C1-C3 alkyl group, and R³ is afluorine atom.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group, R² is a C1-C3 alkyl group, and R³ is a fluorine atom.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group, R² is a methyl group, and R³ is a halogen atom.

A compound represented by the formula (XIII) in which R¹ is a C1-C3alkyl group, R² is a methyl group, and R³ is a fluorine atom.

EXAMPLES

The present invention will be explained in more detail by PreparationExamples, Formulation Examples and Test Examples, but the presentinvention is not limited to these Examples.

First, Preparation Examples of the present compound and ReferencePreparation Examples for preparing intermediates of the present compoundwill be described.

Preparation Example 1

110 mg of methyl4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate and 83.9 mgof 2-aminobenzoimidzole were added to 15 ml of bromobenzene, then, themixture was stirred for 4 hours under heat refluxing condition. Thereaction mixture was cooled to room temperature, then, to the reactionmixture was added 30 ml of n-hexane. The resulting solid was collectedby filtration, and washed with n-hexane and dried to obtain 115 mg ofN-(2-benzimidazolyl)-4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 1) represented by theformula:

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 3.52 (3H, s), 6.28 (1H, d, J=8 Hz), 7.12(2H, m), 7.50 (2H, m), 8.04 (1H, d, J=8 Hz), 12.22 (1H, s), 13.31 (1H,s)

Preparation Example 2

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate andaccording to the same manner as that of Preparation Example 1,N-(2-benzimidazolyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 2) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 2.45 (3H, s), 3.50 (3H, s), 6.26 (1H, s),7.13 (2H, m), 7.48 (2H, m), 12.19 (1H, s), 13.32 (1H, s), 14.28 (1H, s)

Preparation Example 3

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate,using 5-amino-3-trifluoromethyl-1,2,4-thiadiazol in place of2-aminobenzimidazole and according to the same manner as that ofPreparation Example 1,N-(3-trifluoromethyl-1,2,4-thiadiazol-5-yl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 3) was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.44 (3H, s), 3.58 (3H, s), 6.06 (1H, s),13.34 (1H, s), 14.07 (1H, s)

Preparation Example 4

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate,using 2-amino-5-fluorobenzimidazole in place of 2-aminobenzimidazole andaccording to the same manner as that of Preparation Example 1,N-(5-fluoro-2-benzimidazolyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 4) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 2.45 (3H, s), 3.49 (3H, s), 6.26 (1H, s),6.97 (1H, m), 7.26 (1H, m), 7.47 (1H, m), 12.28 (1H, s), 13.37 (1H, s),14.20 (1H, s)

Preparation Example 5

Using 2-amino-5-fluorobenzimidazole in place of 2-aminobenzimidazole andaccording to the same manner as that of Preparation Example 1,N-(5-fluoro-2-benzimidazolyl)-4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 5) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 3.52 (3H, s), 6.27 (1H, d, J=7 Hz), 6.98(1H, m), 7.26 (1H, d, J=7 Hz), 7.47 (1H, m), 8.04 (1H, d, J=8 Hz), 12.31(1 H, s), 13.37 (1H, s), 14.32 (1H, s)

Preparation Example 6

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate,using 2-amino-5-chlorobenzimidazole in place of 2-aminobenzimidazole andaccording to the same manner as that of Preparation Example 1,N-(5-chloro-2-benzimidazolyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 6) was obtained.

¹H-NMR (CD₃SOCD₃, TMS) δ(ppm): 2.45 (3H, s), 3.49 (3H, s), 6.26 (1H, s),7.14 (1H, m), 7.43-7.52 (2H, m), 12.33 (1H, s), 13.40 (1H, s), 14.16 (1H, s)

Preparation Example 7

Using ethyl1-ethoxymethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate inplace of methyl4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate and accordingto the same manner as that of Preparation Example 1,N-(5-fluoro-2-benzimidazolyl)-1-ethoxymethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 7) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 1.12 (3H, t, J=7 Hz), 3.58 (2H, q, J=7Hz), 5.35 (2H, s), 6.31 (1H, d, J=8 Hz), 7.13 (2H, m), 7.47 (2H, m),8.04 (1H, d, J=8 Hz), 12.20 (1H, m), 13.17 (1H, m)

Preparation Example 8

Using a carboxylate compound represented by the formula:

in place of methyl4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate and accordingto the same manner as that of Preparation Example 1, a carboxamidecompound represented by the formula:

(hereinafter, referred to as present compound 8) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 2.15 (2H, m) 3.14 (2H, t, J=8 Hz), 4.07(2H, t, J=7 Hz), 6.26 (1H, s), 7.14 (2H, m), 7.48 (2H, m), 12.20 (1H,bs), 13.22 (1H, s)

Preparation Example 9

Using methyl 1-ethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylatein place of methyl4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate and accordingto the same manner as that of Preparation Example 1,N-(2-benzimidazolyl)-1-ethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 9) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 1.27 (3H, d, J=7 Hz), 4.00 (2H, q, J=7Hz), 6.30 (1H, d, J=7 Hz), 7.14 (2H, m), 7.49 (2H, m), 8.07 (1H, d, J=7Hz), 13.35 (1H, s)

Preparation Example 10

Using 2-amino-4,5-dicyanoimidazole in place of 2-aminobenzimidazole andaccording to the same manner as that of Preparation Example 1,N-(4,5-dicyano-2-imidazolyl)-4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 10) was obtained.

Preparation Example 11

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate,using 3-aminopyrazole in place of 2-aminobenzimidazole and according tothe same manner as that of Preparation Example 1,N-(3-pyrazolyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 11) was obtained.

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 2.51 (3H, s), 3.52 (3H, s), 6.16 (1H, s),6.59 (1H, s), 7.69 (1H, s), 12.58 (1H, s), 12.63 (1H, s)

Preparation Example 12

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate,using 2-amino-5-methyl-1,3,4-thiadiazole in place of2-aminobenzimidazole and according to the same manner as that ofPreparation Example 1,N-(5-methyl-1,3,4-thiadiazol-2-yl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 12) represented by theformula:

was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.41 (3H, s), 2.72 (3H, s), 3.54 (3H, s),6.01 (1H, s), 13.66 (1H, s), 13.80 (1H, s)

Preparation Example 13

Using ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate,using 2-aminothiazole in place of 2-aminobenzimidazole and according tothe same manner as that of Preparation Example 1,N-(2-thiazolyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 13) was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.39 (3H, s), 3.53 (3H, s), 5.99 (1H, s),7.02 (1H, d, J=3 Hz), 7.52 (1H, d, J=3 Hz), 13.49 (1H, s), 14.09 (1H, s)

Preparation Example 14

197 mg of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 76 mg of 2-amino-1,3,4-thiadiazole were added to 2 ml ofbromobenzene, then, the mixture was stirred for 5 hours under heatrefluxing condition. The reaction mixture was cooled to roomtemperature, then, to the reaction mixture was added n-hexane. Theresulting solid was collected by filtration, and washed with a mixtureof t-butyl methyl ether and n-hexane and dried to obtain 183 mg ofN-(1,3,4-thiadiazol-2-yl)-5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 14) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.64 (3H, s), 3.65 (3H, s), 8.90 (1H, s),13.85 (1H, s), 14.63 (1H, s)

Preparation Example 15

Using ethyl5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylatein place of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate,using 2-amino-5-methylthiazole in place of 2-amino-1,3,4-thiadiazole andaccording to the same manner as that of Preparation Example 12,N-(5-methyl-2-thiazolyl)-5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamiderepresented by the formula:

(hereinafter, referred to as present compound 15) was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.42 (3H, s), 2.43 (3H, d, J=3 Hz), 3.54 (3H,s), 7.17 (1H, d, J=1 Hz), 13.32 (1H, s), 14.69 (1H, s)

Preparation Example 16

213 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 94 mgof 2-amino-1,3,4-thiadiazole were added to 2.5 ml of bromobenzene, then,the mixture was stirred for 6.5 hours under heat refluxing condition.The reaction mixture was cooled to room temperature, then, the resultingsolid was collected by filtration, and washed with a mixed solvent oft-butyl methyl ether and hexane and dried to obtain 185 mg of1,6-dimethyl-4-hydroxy-2-oxo-N-(1,3,4-thiadiazol-2-yl)-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 16) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.41 (3H, s), 3.54 (3H, s), 6.01 (1H, s),8.88 (1H, s), 13.67 (1H, s), 13.84 (1H, s)

Preparation Example 17

212 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 117mg of 2-amino-5-ethyl-1,3,4-thiadiazole were added to 2.5 ml ofbromobenzene, then, the mixture was stirred for 5 hours under heatrefluxing condition. The reaction mixture was cooled to roomtemperature. The resulting solid was collected by filtration, and washedwith a mixed solvent of t-butyl methyl ether and hexane and dried toobtain 200 mg ofN-(5-ethyl-1,3,4-thiadiazol-2-yl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 17) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.43 (3H, t, J=8 Hz), 2.41 (3H, s), 3.08 (2H,q, J=8 Hz), 3.53 (3H, s), 6.00 (1H, s), 13.65 (1H, s), 13.81 (1H, s)

Preparation Example 18

243 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 122mg of 2-amino-3-methyl-1,2,4-thiadiazole were added to 2.5 ml ofbromobenzene, then, the mixture was stirred for 5 hours under heatrefluxing condition. The reaction mixture was cooled to roomtemperature. The resulting solid was collected by filtration, and washedwith a mixed solvent of t-butyl methyl ether and hexane and dried toobtain 257 mg of1,6-dimethyl-4-hydroxy-N-(3-methyl-1,2,4-thiadiazol-5-yl)-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 18) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.42 (3H, s), 2.58 (3H, s), 3.54 (3H, s),6.04 (1H, s), 13.53 (1H, s), 13.61 (1H, s)

Preparation Example 19

213 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 120mg of 5-amino-3-ethyl-1,2,4-thiadiazole were added to 2.5 ml ofbromobenzene, then, the mixture was stirred for 4 hours under heatrefluxing condition. The reaction mixture was cooled to roomtemperature. The resulting solid was collected by filtration, and washedwith a mixed solvent of t-butyl methyl ether and hexane and dried toobtain 231 mg of1,6-dimethyl-N-(3-ethyl-1,2,4-thiadiazol-5-yl)-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 19) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.37 (3H, t, J=7 Hz), 2.42 (3H, s), 2.91 (2H,q, J=7 Hz), 3.54 (3H, s), 6.03 (1H, s), 13.55 (1H, s), 13.59 (1H, s)

Preparation Example 20

212 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 105mg of 2-amino-5-methylthiazole were added to 2.5 ml of bromobenzene,then, the mixture was stirred for 5.5 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature. Theresulting solid was collected by filtration, and washed with a mixedsolvent of t-butyl methyl ether and hexane and dried to obtain 188 mg of1,6-dimethyl-4-hydroxy-N-(5-methylthiazol-2-yl)-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 20) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.39 (3H, s), 2.42 (3H, s), 3.52 (3H, s),5.99 (1H, s), 7.16 (1H, s), 13.33 (1H, s), 14.17 (1H, s)

Preparation Example 21

210 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 117mg of 2-amino-4-ethylthiazole were added to 2.5 ml of bromobenzene,then, the mixture was stirred for 5.5 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature. Theresulting solid was collected by filtration, and washed with a mixedsolvent of t-butyl methyl ether and hexane and dried to obtain 150 mg of1,6-dimethyl-N-(4-ethylthiazol-2-yl)-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 21) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.28 (3H, t, J=7 Hz), 2.39 (3H, s), 2.72 (2H,q, J=7 Hz), 3.52 (3H, s), 5.99 (1H, s), 6.57 (1H, s), 13.41 (1H, s),14.14 (1H, s)

Preparation Example 22

223 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 129mg of 2-amino-5-chlorothiazole were added to 2.5 ml of bromobenzene,then, the mixture was stirred for 8.5 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature. Theresulting solid was collected by filtration, and washed with a mixedsolvent of t-butyl methyl ether and hexane and dried to obtain 153 mg ofN-(5-chlorothiazol-2-yl)-1,3-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 22) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.41 (3H, s), 3.53 (3H, s), 6.01 (1H, s),7.33 (1H, s), 13.44 (1H, s), 13.84 (1H, s)

Preparation Example 23

213 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 78 mgof 3-amino-1,2,4-triazole were added to 2.5 ml of bromobenzene, then,the mixture was stirred for 7.5 hours under heat refluxing condition.The reaction mixture was cooled to room temperature. The resulting solidwas collected by filtration, and washed with a mixed solvent of t-butylmethyl ether and hexane and dried to obtain 188 mg of1,6-dimethyl-4-hydroxy-2-oxo-N-(1,2,4-triazol-3-yl)-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 23) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.42 (3H, s), 3.53 (3H, s), 6.02 (1H, s),7.79 (1H, s), 13.29 (1H, s), 13.86 (1H, s)

Preparation Example 24

211 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 90 mgof 3-amino-5-methyl-1,2,4-triazole were added to 2.5 ml of bromobenzene,then, the mixture was stirred for 7 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature. Theresulting solid was collected by filtration, and washed with a mixedsolvent of t-butyl methyl ether and hexane and dried to obtain 214 mg of1,6-dimethyl-4-hydroxy-N-(5-methyl-1,2,4-triazol-3-yl)-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 24) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.38 (3H, s), 2.40 (3H, s), 3.52 (3H, s),6.00 (1H, s), 7.79 (1H, s), 13.19 (1H, s), 13.94 (1H, s)

Preparation Example 25

213 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 79 mgof 3-amino-1-methylpyrazole were added to 2.5 ml of bromobenzene, then,the mixture was stirred for 6.5 hours under heat refluxing condition.The reaction mixture was cooled to room temperature. The resulting solidwas collected by filtration, and washed with a mixed solvent of t-butylmethyl ether and hexane and dried to obtain 134 mg of1,6-dimethyl-4-hydroxy-N-(1-methylpyrazol-3-yl)-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 25) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.37 (3H, s), 3.50 (3H, s), 3.84 (3H, s),5.95 (1H, s), 6.59 (1H, s), 6.61 (1H, d, J=2 Hz), 12.48 (1H, s), 15.25(1H, s)

Preparation Example 26

257 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 260mg of 2-aminoimidazole were added to 5 ml of bromobenzene, then, themixture was stirred for 2 hours under heat refluxing condition. Further,to the mixture was added 151 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate, and theresultant mixture was stirred for 2.5 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature. Theresulting solid was collected by filtration, and washed with a mixedsolvent of t-butyl methyl ether and hexane and dried to obtain 580 mg of1,6-dimethyl-4-hydroxy-N-(2-imidazolyl)-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 26) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.39 (3H, s), 3.52 (3H, s), 5.98 (1H, s),6.85 (1H, d, J=1 Hz), 6.90 (1H, d, J=1 Hz), 10.60 (1H, s), 13.06 (1H,s), 14.29 (1H, s)

Preparation Example 27

213 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 79 mgof 3-amino-5-methylisooxazole were added to 2.5 ml of bromobenzene,then, the mixture was stirred for 6.5 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature. Theresulting solid was collected by filtration, and washed with a mixedsolvent of t-butyl methyl ether and hexane and dried to obtain 141 mg of1,6-dimethyl-4-hydroxy-N-(5-methylisooxazol-3-yl)-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 27) represented by theformula:

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 2.42 (3H, s), 2.42 (3H, s), 3.51 (3H, s),5.98 (1H, s), 6.66 (1H, s), 12.72 (1H, s), 14.65 (1H, s)

Preparation Example 28

199 mg of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 98 mg of 2-amino-benzimidazole were added to 2 ml of bromobenzene,then, the mixture was stirred for 9.5 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature, then,hexane was added to this and the resultant mixture was allowed to standstill. The resulting solid was collected by filtration, and washed witha mixture of t-butyl methyl ether and n-hexane and dried to obtain 202mg ofN-(2-benzimidazolyl)-5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 28) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.62 (3H, s), 3.63 (3H, s), 7.18-7.72 (5H,m), 10.76 (1H, s), 13.41 (1H, s)

Preparation Example 29

161 mg of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 51 mg of 3-amino-1,2,4-triazole were added to 1.5 ml ofbromobenzene, then, the mixture was stirred for 5 hours under heatrefluxing condition. The reaction mixture was cooled to roomtemperature, then, hexane was added to this and the resultant mixturewas allowed to stand still. The resulting solid was collected byfiltration, and washed with a mixture of t-butyl methyl ether andn-hexane and dried to obtain 153 mg of5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-N-(1,2,4-triazol-3-yl)-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 29) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.64 (3H, s), 3.63 (3H, s), 7.81 (1H, s),13.30 (1H, s), 14.80 (1H, s)

Preparation Example 30

160 mg of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 60 mg of 2-aminothiazole were added to 1.5 ml of bromobenzene, then,the mixture was stirred for 5 hours under heat refluxing condition. Thereaction mixture was cooled to room temperature, then, hexane was addedto this and the resultant mixture was allowed to stand still. Theresulting solid was collected by filtration, and washed with a mixtureof t-butyl methyl ether and n-hexane and dried to obtain 136 mg of5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-N-(2-thiazolyl)-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 30) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.62 (3H, s), 3.62 (3H, s), 7.05 (1H, d, J=3z), 7.54 (1H, d, J=3 Hz), 13.48 (1H, s), 15.07 (1H, s)

Preparation Example 31

200 mg of5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylicacid was dissolved in 3 ml of acetonitrile, and 162 mg ofcarbonyldiimidazole was added to this. The mixture was stirred for 1hour under heat refluxing condition, then, 114 mg of2-amino-4-methylthiazole was added, and the resulting mixture wasfurther stirred for 1 hour under heat refluxing condition. Thereafter,the reaction mixture was cooled to room temperature. As a result, acrystal was produced. The produced crystal was collected by filtration,to obtain 90 mg of5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-N-(4-methyl-2-thiazolyl)-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 31) represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.29 (3H, s), 2.43 (3H, s), 3.50 (3H, s),6.97 (1H, s), 13.75 (1H, s), 14.37 (1H, s)

Then, Reference Preparation Examples for preparing intermediates of thepresent compound will be described.

Reference Preparation Example 1

At room temperature, 7.9 ml of trimethylsilylazide was added to amixture of 5.0 g of maleic anhydride and 20 ml of benzene. The mixturewas stirred at 50-60° C. for 3 hours. After cooling the reaction mixtureto room temperature, 4.5 ml of ethanol was added, followed by stirringfor additional 3 hours. The resulting solid was collected by filtration,and washed with diethyl ether to obtain 300 mg of2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

¹H-NMR (CD₃SOCD₃, TMS) δ (ppm): 5.62 (1H, d, J=8 Hz), 7.66 (1H, d, J=8Hz), 11.55 (1H, s)

Reference Preparation Example 2

At room temperature, 50.0 g of trimethylsilylazide was added to amixture of 44.8 g of citraconic anhydride and 60 ml of chloroform. Themixture was stirred at 50-60° C. for 5 hours. After cooling the reactionmixture with an ice, 25.0 g of ethanol was added, followed by stirringfor additional 30 minutes. The resulting solid was collected byfiltration, and washed with a mixed solvent of chloroform and ethanol toobtain crude 4-methyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

Further, the washing solution was concentrated under reduced pressure.T-butyl methyl ether was added to the residue, followed by filtration.The resulting solid was washed with t-butyl methyl ether. The filtrateand the washing solution were combined and concentrated under reducedpressure to obtain crude 5-methyl-2H-1,3-oxazine-2,6(3H)-dionerepresented by the formula:

4-Methyl-2H-1,3-oxazine-2,6(3H)-dione

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 2.06 (3H, s), 5.50 (1H, s), 11.47 (1H,s-br)

5-Methyl-2H-1,3-oxazine-2,6(3H)-dione

¹H-NMR(CD₃SOCD₃, TMS) δ(ppm): 1.78 (3H, s), 7.48 (1H, s), 11.47 (1H,s-br)

Reference Preparation Example 3

At room temperature, 1.50 g of 2H-1,3-oxazine-2,6(3H)-dione, 2.19 g ofpotassium carbonate and 3.77 g of methyl iodide were sequentially addedto 30 ml of acetone, and the mixture was stirred for 10 hours under heatrefluxing condition. The reaction mixture was cooled to room temperatureand filtered. The filtrate was concentrated under reduced pressure, andthe resulting solid was dried to obtain 1.46 g of3-methyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

¹HNMR(CD₃SOCD₃, TMS) δ(ppm): 3.26 (3H, s), 5.68 (1H, d, J=8 Hz), 7.82(1H, d, J=8 Hz)

Reference Preparation Example 4

Using crude 4-methyl-2H-1,3-oxazine-2,6(3H)-dione in place of2H-1,3-oxazine-2,6(3H)-dione and according to the same manner as that ofReference Preparation Example 3, crude3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.27 (3H, d), 3.41 (3H, s), 5.49 (1H, d)

Reference Preparation Example 5

Using ethyl bromide in place of methyl iodide and according to the samemanner as that of Reference Preparation Example 3,3-ethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

Reference Preparation Example 6

Using chloromethyl ethyl ether in place of methyl iodide and accordingto the same manner as that of Reference Preparation Example 3,3-ethoxymethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

Reference Preparation Example 7

Using crude 5-methyl-2H-1,3-oxazine-2,6(3H)-dione in place of2H-1,3-oxazine-2,6(3H)-dione and according to the same manner as that ofReference Preparation Example 3, crude3,5-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.94 (3H, d), 3.37 (3H, s), 6.99 (1H,q-like)

Reference Preparation Example 8

Using 4,5-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

in place of 2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 3,3,4,5-trimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.97 (3H, s), 2.26 (3H, s), 3.42 (3H, s)

Reference Preparation Example 9

Under ice cooling, 568 mg of sodium hydride (60%) was added to a mixtureof 181 mg of dimethyl malonate and 70 ml of N,N-dimethylformamide andthe mixture was stirred for 20 minutes. After the mixture was heated to80° C., 1.50 g of 3-methyl-2H-1,3-oxazine-2,6(3H)-dione was added to themixture, followed by further stirring at 120° C. for 7 hours. Thereaction mixture was concentrated under reduced pressure, 2 mol/Lhydrochloric acid was added to the residue, and the mixture was stirredat 60° C. for 15 minutes. The mixture was extracted with ethyl acetate.The organic layer was washed with an aqueous saturated sodium chloridesolution, dried with sodium sulfate, filtered, and concentrated. Theresidue was subjected to silica gel column chromatography (eluent: ethylacetate) to obtain 100 mg of methyl4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate representedby the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.44 (3H, s), 3.97 (3H, s), 5.97 (1H, d,J=8 Hz), 7.37 (1H, d, J=8 Hz), 13.21 (1H, s)

Reference Preparation Example 10

At room temperature, 1 ml of a solution of 0.71 g diethyl malonate intetrahydrofuran was added to a mixture of 0.19 g of sodium hydride and 4ml of tetrahydrofuran and the mixture was stirred for 20 minutes. Atroom temperature, 3 ml of a solution of 0.59 g3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione in tetrahydrofuran was addedto the mixture, followed by stirring for 2 hours under heat refluxingcondition. The reaction mixture was concentrated under reduced pressure.To the residue, 10 ml of water and 12 ml of 2 mol/L hydrochloric acidwere added, followed by extraction with ethyl acetate. The organic layerwas dried with magnesium sulfate, then filtered and concentrated toobtain 0.57 g of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.44 (3H, t, J=7 Hz), 2.34 (3H, s), 3.45 (3H,s), 4.43 (2H, q, J=7 Hz), 5.86 (1H, s), 13.26 (1H, s)

Reference Preparation Example 11

Using 3-ethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and using dimethyl malonate inplace of diethyl malonate and according to the same manner as that ofReference Preparation Example 10, methyl1-ethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate represented bythe formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.33 (3H, t, J=7 Hz), 3.94 (2H, q, J=7 Hz),3.98 (3H, s), 5.98 (1H, d, J=8 Hz), 7.37 (1H, d, J=8 Hz), 13.25 (1H, s)

Reference Preparation Example 12

Using 3-ethoxymethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 10, ethyl1-ethoxymethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (3H, t, J=7 Hz), 1.44 (3H, t, J=7 Hz),3.60 (2H, q, J=7 Hz), 4.45 (2H, q, J=7 Hz), 5.30 (2H, s), 6.03 (1H, d,J=8 Hz), 7.50 (1H, d, J=8 Hz), 13.55 (1H, s)

Reference Preparation Example 13

Using 3,5-dimethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 10, ethyl1,5-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

Reference Preparation Example 14

Using 3,4,5-trimethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione, using dimethyl malonate inplace of diethyl malonate and according to the same manner as that ofReference Preparation Example 10, methyl4-hydroxy-2-oxo-1,5,6-trimethyl-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.05 (3H, s), 2.36 (3H, s), 3.51 (3H, s),3.96 (3H, s), 13.83 (1H, s)

Reference Preparation Example 15

A mixture of 10.1 ml 2-methyl-1-pyrroline and 2.27 ml triethylmethanetricarboxylate was stirred at 200° C. for 20 hours. The reactionmixture was cooled to room temperature and subjected to silica gelcolumn chromatography to obtain 400 mg of carboxylic ester representedby the formula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.43 (3H, t, J=7 Hz), 2.14 (2H, m), 3.06 (2H,t, J=7 Hz), 4.08 (2H, t, J=7 Hz), 4.41 (2H, q, J=7 Hz), 5.90 (1H, s),13.35 (1H, s)

Reference Preparation Example 16

After 16.5 g of ethyl 2-chloroacetoacetate and 8.91 g of ethyl carbamatewere sequentially added to 83.9 g of phosphorus oxychloride, this wasstirred at 90° C. for 5 hours. The reaction mixture was concentratedunder reduced pressure, and toluene and water were added to the residue,followed by separation of the layers. The organic layer was extractedwith water four times. The aqueous layer was collected and extractedwith ethyl acetate four times. The organic layer was collected, washedwith water, dried with magnesium sulfate, filtered and concentrated. Theresulting solid was washed with a mixture of t-butyl methyl ether andn-hexane and dried to obtain5-chloro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

¹H-NMR (CDCl₃, TMS) δ(ppm): 2.34 (3H, s)

Reference Preparation Example 17

At room temperature, 2.11 g of5-chloro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione, 2.07 g of potassiumcarbonate and 1.3 ml of methyl iodide were sequentially added to 40 mlof acetone, then the mixture was stirred for 3 hours under heatrefluxing condition. To the reaction mixture was added 0.5 ml of methyliodide, and the mixture was further stirred for 2 hours under heatrefluxing condition. The reaction mixture was cooled to room temperatureand filtered. The filtrate was concentrated under reduced pressure. Theresulting solid was dried to obtain 1.74 g of5-chloro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.48 (3H, s), 3.48 (3H, s)

Reference Preparation Example 18

To 0.43 g of sodium hydride (60%) was added 35 ml of tetrahydrofuran,2.5 ml of a solution of 1.76 g diethyl malonate in tetrahydrofuran wasfurther added under ice cooling, and the mixture was stirred at roomtemperature for 1 hour. To the mixture was added 1.74 g of5-chrolo-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione, and this was stirredfor 3.5 hours under heat refluxing condition. The reaction mixture wasconcentrated under reduced pressure. To the residue, 20 ml of water and15 ml of 1 mol/L hydrochloric acid were sequentially added, followed byextraction with 85 ml of chloroform twice. The organic layer was driedwith magnesium sulfate, filtered, and concentrated. The residue waswashed with n-hexane to obtain 1.52 g of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxlaterepresented by the formula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.45 (3H, t, J=7 Hz), 2.57 (3H, s), 3.54 (3H,s), 4.46 (2H, q, J=7 Hz), 14.10 (1H, s)

Reference Preparation Example 19

Using ethyl 2-fluoroacetoacetate in place of ethyl 2-chloroacetoacetateand according to the same manner as that of Reference PreparationExample 16, 5-fluoro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione representedby the formula:

was obtained.

Reference Preparation Example 20

Using 5-fluoro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione in place of5-chloro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 17,5-fluoro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

was obtained.

Reference Preparation Example 21

Using 5-fluoro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione in place of5-chloro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and according to thesame manner as that of Reference Preparation Example 18, ethyl5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.45 (3H, d, J=7 Hz), 2.38 (3H, s), 3.46 (3H,s), 4.46 (2H, q, J=7 Hz), 13.67 (1H, s), 13.64 (1H, s)

Reference Preparation Example 22

14.4 g of a compound represented by the formula (XVII):

and 6.8 g of diketene were dissolved in 150 ml of acetonitrile, and 1.01g of triethylamine was added at room temperature. The mixture wasstirred at room temperature for 1 hour. Then, 15.5 g of a 40%methylamine solution in methanol was added to the mixture, then this wasstirred at room temperature for 1 hour. Thereafter, the reaction mixturewas cooled with an ice, and 30 ml of concentrated hydrochloric acid wasadded. The resulting crystal was collected by filtration and dried toobtain 17.6 g of2,2-dimethyl-5-(1-hydroxy-3-methylamino-2-butenylidene)-1,3-dioxane-4,6-dionerepresented by the formula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 1.70 (6H, s), 2.16 (3H, s), 3.09 (3H, d, J=4Hz), 6.45 (1H, s), 8.82 (1H, br)

Reference Preparation Example 23

1.0 g of2,2-dimethyl-5-(1-hydroxy-3-methylamino-2-butenylidene)-1,3-dioxane-4,6-dionewas suspended in 20 ml of acetonitrile, 806 mg ofN,N′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) was addedthereto, and this was stirred at room temperature for 1 hour and at 50°C. for 30 minutes. The reaction mixture was added to 100 ml of ice waterand extracted with 100 ml of chloroform twice. The organic layer wasdried with anhydrous magnesium sulfate and concentrated, and the residuewas subjected to silica gel column chromatography (eluent:ethyl acetate)to obtain 480 mg of5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylicacid represented by the formula:

¹H-NMR(CDCl₃, TMS) δ(ppm): 2.47 (3H, s), 3.58 (3H, s), 13.89 (1H, br),15.46 (1H, br)

Then, Formulation Examples will be shown. Part represents part byweight.

Formulation Example 1

Fifty parts of each of the present compounds 1 to 13, 3 parts of calciumligninsulfonate, 2 parts of sodium laurylsulfate, and 45 parts ofsynthetic hydrous silicon oxide are ground and mixed well to obtain eachwettable powder.

Formulation Example 2

Twenty parts of each of the present compounds 1 to 13, and 1.5 parts ofsorbitan triolate are mixed with 28.5 parts of an aqueous solutioncontaining 2 parts of polyvinyl alcohol, and finely-divided by a wetgrinding method, 40 parts of an aqueous solution containing 0.05 part ofxanthan gum and 0.1 part of aluminum magnesium silicate are added, 10parts of propylene glycol is added and this is stirred and mixed toobtain each flowable preparation.

Formulation Example 3

Two parts of each of the present compounds 1 to 13, 88 parts of kaolinclay and 10 parts of talc are ground and mixed well to obtain each dust.

Formulation Example 4

Five parts of each of the present compounds 1 to 13, 14 parts ofpolyoxyethylene styryl phenyl ether, 6 parts of calciumdodecylbenzenesulfonate and 75 parts of xylene are mixed well to obtaineach emulsifiable concentrate.

Formulation Example 5

Two parts of each of the present compounds 1 to 13, 1 part of synthetichydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts ofbentonite and 65 parts of kaolin clay are ground and mixed well, wateris added, and the mixture is kneaded well, granulated and dried toobtain each granule.

Formulation Example 6

Ten parts of each of the present compounds 1 to 13, 35 parts of whitecarbon containing 50 parts of polyoxyethylene alkyl ether sulfateammonium salt and 55 parts of water are mixed, and finely-divided by awet grinding method to obtain each flowable preparation.

Then, Test Example demonstrates that the present compound is useful asan agricultural and horticultural fungicide. The present compound isindicated by a compound number.

Test Example 1 Cucumber Grey Mold Controlling Effect Test (PreventiveEffect)

A plastic pot was charged with a sand loam, and cucumber (Name of plantvariety: Sagamihanpaku) was seeded, and grown for 10 days in agreenhouse. Each flowable preparation of the present compounds 1 to 9,12 to 17, 20, 23 to 25, 27 and 31 which had been obtained according toPreparation Example 6 was diluted with water to a predeterminedconcentration (500 ppm), to prepare a spraying solution. Each sprayingsolution was foliage-sprayed so that the solution was sufficientlyadhered to cucumber leaves. After spraying, the cucumber was air-driedto an extent that the spraying solution on the leaves was dried, and aPDA medium containing a spore of cucumber grey mold (Botrytis cinerea)was placed on the cucumber leaves. After inoculation, the cucumber wasplaced at 12° C. under high humidity for 5 days, and controlling effectwas investigated. As a result, an area of lesion in a plant treated withthe present compounds 1 to 9, 12 to 17, 20, 23 to 25, 27 and 31 was 10%or less of an area of a lesion in a non-treated plant.

Test Example 2 Wheat Scab (Fusarium culmorum) Controlling Effect Test(Preventive Effect)

A plastic pot was charged with a sand loam, and a wheat (Name of plantvariety: Shirogane komugi) was seeded, and was grown for 8 days in agreenhouse. Each flowable preparation of the present compound 12, 13 and15 which had been obtained according to Preparation Example 6 wasdiluted with water to a predetermined concentration (500 ppm) to preparea spraying solution. Each spraying solution was foliage-sprayed so thatthe solution was sufficiently adhered to the above adhered to wheatleaves. After spraying, the wheat was air-dried to an extent that thespraying solution on the leaves was dried, then a spore suspension ofwheat scab (Fusarium culmorum) (containing about 2000000 spores per 1 mlof the suspension) was spraying-inoculated (at a ratio of about 2 ml perone plant). After inoculation, the wheat was placed at 23° C. under highhumidity for 4 days, then placed in a 23° C. greenhouse for 3 days.Thereafter, the controlling effect was investigated. As a result, anarea of a lesion in a plant treated with the present compound 12, 13 and15 was 10% or less of an area of a lesion in a non-treated plant.

INDUSTRIAL APPLICABILITY

By using the present compound, a plant disease can be controlled.

1. A carboxamide compound represented by the formula (I):

wherein Q represents a 2-thiazolyl group optionally substituted with atleast one group selected from the group consisting of a halogen atom, acyano group, a C1-C3 alkyl group and a C1-C3 haloalkyl group, R¹represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group, R²represents a hydrogen atom or a C1-C3 alkyl group, and R³ represents ahydrogen atom, a halogen atom or a C1-C3 alkyl group.
 2. The carboxamidecompound according to claim 1, wherein R³ is a hydrogen atom or a C1-C3alkyl group.
 3. The carboxamide compound according to claim 1, whereinR³ is a hydrogen atom or a halogen atom.
 4. A plant disease controllingcomposition comprising the carboxamide compound as defined in claim 1 asan active ingredient, and an inert carrier.